15

Chapter
POLYMERS

NCERT CRUX

Introduction Classification of Polymer

The word ‘polymer’ is coined from two Greek words: ‘poly’ On the basis of source (from which polymer is derived these
means many and ‘mer’ means unit or part. are of three types-
Polymers are very high molecular mass substances (103 – 107 u) (i) Natural polymer Ex. Cellulose, starch
where each molecule is obtained from very large number of (ii) Semi-synthetic polymer Ex. Rayon
simple molecules joined together in a regular way. This simple (iii) Synthetic polymer Ex. Nylon-6, 6
molecule is monomer and the process of formation of
polymers from simple molecule is polymerization. Eg.
nCH
= 2 CH 2 
→ –[ CH 2 – CH 2−] n
ethene polyethene

Table: Some important Polymers

S.
Name of Polymers Monomer Structure Uses
No.
Polyethylene CH2=CH2 Film wrap, plastic
1.
(low density (LDPE)) (ethylene) bags
Polypropylene CH2=CHCH3
2. Carpet, upholstery
(PP) different grades (propylene)

CH2=CHCl
3. Polyvinyl chloride (PVC) Pipes, siding, flooring
(vinyl chloride)

Poly(vinylidene chloride) CH2=CCl2

4. Seat covers, films
(Saran A) (vinylidene chloride)

Polystyrene (PS) CH2=CHC6H5 Toys, cabinets pack-

5.
(Styron) (styrene) aging (foamed)

Polyacrylonitrile CH2=CHCN Rugs, blankets

6.
(PAN, Orlon, Acrilan) (acrylonitrile) clothing

Polytetrafluoroethylene CF2=CF2 Non-stick surfaces,

7.
(PTFE, Teflon) (tetrafluoroethylene) electrical insulation
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S.
Name of Polymers Monomer Structure Uses
No.
F2C=CFCl For making non-stick
Polychlorotrifluoro ethylene
8. Chlorotrifluoro utensils, coating mak-
(PCTFP)
ethylene ing etc.
Poly(methyl methacrylate)
CH2=C(CH3)CO2CH3 lighting covers, signs
9. (PMMA, Lucite, Plexiglass,
(methyl methacrylate) skylights
perspex)
Poly(vinyl acetate) CH2=CHOCOCH3 latex paints,
10.
(PVAc) (vinyl acetate) adhesives

CH2=CH– requires
11. C(CH3)=CH2 vulcanization
(isoprene) for practical use

1,3- butadiene + Packaging,

12. Buna N
acrylonitrite Orthopaedic devices

2-chloro-1-3 Manufacturing of
butadiene convey belts, gasket
13. Neoprene and hoses
(Chloroprene)

Biodegradable.
Glycine + Amino
14. Nylon 2,6 Bristles for tooth
caproic acid
brushes, synthesis of
( CH2)5 artificial fibres

Poly b – Hydroxy butyrate- 3–Hydroxybutanoic

Packaging,
15. Co-b-hydroxy valerate acid + 3-hydroxy
Orthopaedic devices
(PHBV) pentanoic acid

Manufacture of floor
1,3 butadiene +
16. Buna S tiles, footwear, cable
styrene
insulation etc.

Melamine + Unbreakable
17. Melamine - formaldehyde
formaldehyde crockery

Tyre cords, fabrics &

18. Nylon 6 Caprolactum
ropes

Hexamethylene
Making of sheets ,
19. Nylon 6,6 diamine + adipic
for brushes & textile.
acid
Polymers 3

S.
Name of Polymers Monomer Structure Uses
No.
HOOC–(CH2)8–
20. Nylon 6,10 COOH Electric insulators
H2N–(CH2)6–NH2
para HO2C–C6H4–
CO2H
21. Polyamide Kevlar + Bulletproof Jackets
para H2N–C6H4–
NH2
HO2C–C6H4–CO2H
(Phthalic acid)
Manufacture of
+
22. Glyptal or Alkyds resin paints and lacquers
HO–CH2CH2–OH
Ethylene glycol

HO2C–C6H4–CO2H
(Terephthalic acid) Used in curtains
Polyester/Dacron/Terylene/
23. + dress fabrics
Mylar
HO–CH2CH2–OH
Ethylene glycol

Used in Kitchen
24. Melamine formaldehyde resin
wares

 Obtained by the polymerisation of ethene under

Types of Polymerisation Reaction high pressure of 1000 to 2000 atm at a temperature
of 350 k - 570 k in presence of traces of peroxide
These are two broad types of polymerisation reaction: initiator (catalyst). It has highly branched structure.
(A) Addition or Chain growth polymerisation.  Chemically inert and tough but flexible & poor
Mechanism: conductor of electricity used in insulation of electricity
(a) Chain initiation steps: carrying wires and manufacture of squeeze bottles
O O O etc.
C6H5— C — O — — O — C — C6H5 2C6H5— C — O 2C6H5 ⇒ High density polythene (HDP)
Benzoyl Peroxide Phenyl radical
 Obtained by addition polymerisation of ethene in

C6H5+ H2C = CH2 C6H5– CH2 – CH2
presence of Ziegler - Natts Catalyst [(C2H5)3 Al +
(b) Chain propagation step Ticly] at a temperature of 333 k - 343 k and pressure
C6H5– CH2 – CH2 + CH2 = CH2
— C6H5 – CH2 – CH2– CH2–CH2 of 6 - 7 atm. It has linear structure.
 Chemically inert and more tough & hard. Used in
H5C6 –( CH2–CH2–) n CH2– CH2 the manufacturing of buckets, pipes etc.
(c) Chain termination step
(ii) Polytetrafluoroethene (Teflon)
C6H5 –( CH2–CH2–) n CH2–CH2 H5C6 –( CH2– CH2–) n CH2
It is manufactured by heating tetrafluoroethene with a
+ – CH2 –( CH2– CH2–) n C6H5
free radical at high pressure. It is also chemically inert
C6H5 –( CH2–CH2–) n CH2–CH2 (Polythene)
and used in making oil seals and gaskets and also used
Ex. Some important addition polymer
for non, stick surface coated utensils.
(i) Polythene - There are two types of polythene Catalyst
⇒ Low density polythene (LDP) n CF2 = CF2 High P.
–CF
[ 2 – CF2–] n
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(iii) Polyacrylonitrile 3. Glyptal/Alkyd Resins: Monomer - Phthalic acid +

The addition polymerisation of acrylonitrile in Ehylene glycol.
presence of a peroxide catalyst leads to the formation
Polyacrylonitrile
CN
Peroxide catalyst
nCH2 = CHCN –CH
[ 2 – CH –] n
It is used as a substitute for wool in making commercial
fibres as orlon or acrilan.
(B) Condensation or step-growth polymerisation.
It involves repetitive condensation reaction between two
bifunctional or trifunctional mono-meric units and results
in the loss of some simple molecules as water, alcohol, Fig.: Poly (ethylene phthalate)
hydrogen chloride etc. Ex. Terylene or dacron.
 It is a copolymer, linear, step growth, three
Some Important Condensation Polymers dimensional cross linked polyester polymer,
1. Polyamides dissolves in suitable solvent.
 These polymers possessing amide linkages are  On evaporation leaves a tough and non flexible film.
important examples of synthetic fibres and are termed 4. Phenol - formaldehyde polymer (Bakelite and related
polymers)
as nylons.
(a) Preparation of nylons
(i) Nylon 6, 6

(ii) Nylon 6  Novolac on heating with formaldehyde undergoes

cross linking to form an infusible solid mass called
bakelite. It is Thermosetting polymer which cannot
be reused or remoulded.
 Bakelite is used for making combs, phonograph
records, electrical switches and handles of various
utensils.

2. Polyesters
 Dacron fibre (terylene) is crease resistant and is used
in blending with cotton and wool fibres and also as
glass reinforcing materials in safety helmets, etc.

5. Melamine – formaldehyde polymer

 It is a copolymer, step growth, linear. It is a fibre with

low moisture content, not damaged by pest like moths.  It is used in the manufacture of unbreakable crockery.
Polymers 5

Copolymerisation  In the manufacture of tyre rubber, 5% of sulphur is

 Copolymerisation is a polymerisation reaction in which used as a cross linking agent.
a mixture of more than one monomeric species is 2. Synthetic rubbers
allowed to polymerise and form a copolymer.
 Synthetic rubber is any vulcanisable rubber like
 The copolymer can be made not only by chain growth polymer, which is capable of getting stretched to
polymerisation but by step growth polymerisation also.
twice its length. e.g Neoprene and Buna-N
 It contains multiple units of each monomer used in the
same polymeric chain.
 Key Note
 For example, a mixture of 1, 3 – butadiene and styrene
can form a copolymer.  Increasing the amount of sulphur makes the
vulcanized polymer harder and more durable.
 Adding 3-5% sulphur makes a product good for
rubber bands and inner tubes.
 Adding 20-30% sulphur makes a hard rubber that
was once widely used in ways that a hard synthetic
plastic is used today.

Biodegradable Polymers
Rubber
1. Natural rubber  These polymers contain functional groups similar to the
 It is manufactured from rubber latex which is a functional groups present in biopolymers.
colloidal dispersion of rubber in water. This latex is  Aliphatic polyesters are one of the important classes
obtained from the rubber which is found in India, Sri- of biodegradable poylmers. Some examples are given
lanka, Indonesia. below:
 Natural rubber may be considered as a linear (A) Poly β-hydroxybutyrate – co– β-hydroxy Valerate
polymer of isoprene (2-methyl-1, 3-butadiene) and
(PHBV)
is also called as cis - 1, 4 - polyisoprene.
 It is obtained by the copolymerisatin of
3-hydroxybutanoic acid.
 PHBV is used in speciality packaging, orthopaedic
Fig.: Isoprene devices and in controlled release of drugs.
 PHBV undergoes bacterial degradation in the
environment.
(B) Nylon-2-nylon-6
Fig.: Natural rubber It is an alternating polyamide copolymer of glycine
(H2N–CH2 –COOH) and amino caproic acid
Vulcanization of Rubber [H2N(CH2)5COOH].
 Natural rubber becomes soft at high temperature (>335
K) and brittle at low temperatures (<283 K) and shows
high water absorption capacity.

 It is step-growth copolymer.
(C) Poly Glycolic Acid (PGA) and Poly Lactic Acid (PLA)
Fig.: Structures of Vulcanised Rubber
This copolymer is commercially called DEXTRON
 It is soluble in non-polar solvents and is non-resistant to
attack by oxidising agents.
 On vulcanisation, sulphur forms cross links at the reactive
sites of double bonds and thus the rubber gets stiffened.
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2. Weight Average Molecular Mass

 Key Note
m1M1 + m 2 M 2 – m3M 3 N1M 21 – N 2 M 22 + N3M32 + ...
A copolymer of PGA and PLA (90 : 10) was the first Mw = =
m1 + m 2 + m3 + ... N1M1 + N 2 M 2 + N3M 3 ....
biodegradable polyester used for stitching of wounds after
Where N1, N2, N3.... etc. are the number m1, m2, m3 are
operation. the masses of macromolecules with molecular masses M1,
M2, M3 of respectively.
3. Poly Dispersity Index (PDI)
Molecular Mass of Polymer PDI = M w / M n

 Key Note
1. Number Average Molecular Mass
 Natural polymers are also called monodisperse polymers
M n = N1M1 – N 2 M 2 – N3M3 – ... since their molecules have same or a narrow range of
N1 + N 2 + N3 + .... molecular masses for natrual polymers PDI = 1.
Where N1, N2, N3 etc are the number of macromolecules  Synthetic polymers are also called poly disperse
polymers. Since their molecules have a wide range
with molecular masses M1, M2 M3 etc. respectively. of molecular masses. For synthetic polymers, PDI > 1